Difunctional sulfones



United States Patent Office 3,492,316 DIFUNCTIQNAL SULFONES Joe T.Adams, St. Albans, and Herman F. Lykins, South Charleston, W. Va.,assignors to Union Carbide Corporation, a corporation of New York NoDrawing. ()riginal application July 10, 1963, Ser. No. 294,161, nowPatent No. 3,312,522, dated Am. 4, 1967. Divided and 610,747

lnt. Cl.

C07d 1/00; D0611! 13/10 US. Cl. 26t)-348 Claims ABSTRACT OF THEDISCLOSURE This is a division of application Ser. No. 294,161, filedJuly 10, 1963, now Patent No. 3,312,522, issued Apr. 4, 1967.

The present invention relates to sulfone compounds which are newcompositions of matter and specifically to certain novel difunctionalsulfones which are useful in the treatment of cellulosic fabrics toimpart shrink resistance and wash-and-wear properties thereto.

It is well known that cotton and other cellulosic fabrics can be treatedwith various polyfunctional cross-linking agents, resins and the like toprovide a fabric which is wrinkle and shrink resistant and which willmaintain a crease for applications such as mens trousers, pleated skirtsand the like. However, many of these methods have been found unsuitablebecause of their lack of permanence. For example, fabrics treated withpolyhydroxy urea resins, such as dimethylol ethylene urea, are subjectto degradation under the conditions present in many commerciallaundering processes, and lose their wrinkle resistance and ability toretain a sharp crease after only a few launderings. Other resinousmaterials, which coat the cellulosic fibers, impart an undesirable harshand boardy hand to the fabric. In addition, because the treatments ofthe prior art generally comprise the addition of the treating agent tothe fabric followed by a one-step cure, usually accomplished attemperatures employed in pressing garments made from the treated fabric,the treatment must be effected by the garment manufacturer when acreased garment is desired. Finally, because the curing occurs duringthe pressing of the garment, errors in pressing cannot be easilyrectified by repressing.

It has been found by this invention, however, that when a cellulosicfabric is impregnated with certain difunctional sulfones, as hereinafterdefined, one functional group of which reacts with cellulose under acidconditions and the other functional group of which reacts With celluloseunder basic conditions, many of the foregoing disadvantages areobviated. Because the sulfones employed in accordance with thisinvention contain no nitrogen they aer not subject to degradation duringlaundering as are the nitrogen-containing resins. Because the sulfonesreact with the cellulose rather than forming a resin coating, thetreated fabric does not have a harsh and boardy hand, but rather, itretains the hand of the untreated fabric.

this application Jan. 23, 1967, Ser. No.v

3,492,316 Patented Jan. 27, 1970 Moreover, because the sulfone can bepermanently incorporated in the cellulosic fabric without alsocrosslinking the fabric, the treatment of this invention, except for thefinal cross-linking, can be conducted by the textile manufacturer.Finally, because the fabric can be pressed without also causing thefinal cross-linking, any errors in pressing can be easily rectified.

The difunctional sulfones which are employed in accordance with thisinvention have the general formula ASO B wherein A is a functional groupwhich will react with a hydroxyl group under acidic conditions (a pH ofabout 6 or less), such as a group containing a vie-epoxy group; and B isa functional group which will react with a hydroxyl group under basicconditions (a pH of about 8 or higher), such as a vinyl group, afi-hydroxalkyl group or a B-(alkoxy)alkyl group. More specifically, thecompounds employed in this invention have the formula RSO CH (R O),,Rwherein R is a vinyl group, a B- hydroxyalkyl grou of from 2 to about 4carbon atoms, inclusive, or a ,B-(alkoxy)alkyl group having from 1 toabout 4 carbons, inclusive, in the alkoxy group thereof and from 2 toabout 4 carbons, inclusive, in the alkylene group thereof; R is adivalent alkylene group of from 1 to about 3 carbons, inclusive; R is avic.-epoxyalkyl group of from 2 to 8 carbons, inclusive; and n is aninteger having a value of 0 or 1. As examples of suitable difunctionalsulfones one can mention epoxyalkyl vinyl sulfones such as2,3-epoxypropyl vinyl sulfone, 3,4-epoxybutyl vinyl sulfone,2,3-epoxybutyl vinyl sulfone, 2-methyl-2,3- epoxypropyl vinyl sulfone,2,3-epoxyhexyl vinyl sulfone 5,6-epoxyhexyl vinyl sulfone and the like;(epoxyalkoxy)alkyl vinyl sulfones such as 2 (epoxyethoxy) ethyl vinylsulfone, 2-(epoxyethoxy)propyl vinyl sulfone,Z-(epoxyethoxy)-l-methylpropyl vonyl sulfone, 2 (2,3- epoxypropoxy)ethylvinyl sulfone, 2 (5,6-epoxyhexoxy) ethyl vinyl sulfone; epoxyalkyl and(epoxyalkoxy)alkyl fi-hydroxyalkyl sulfones such as 2,3-epoxypropyl2-hydroxyethyl sulfone, 2,3-epoxypropyl 2-hydroxypropyl sulfone,2,3-epoxy propyl 2-hydroxy-1-methylpropyl sulfone,2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone and the like; andepoxyalkyl and (epoxyalkoxy)alkyl p-(alkoxy)alkyl sulfones such as2,3-epoxypropyl 2- (methoxy)ethyl sulfone, 2,3-epoxypropyl 2-(ethoxy)ethyl sulfone, 2,3-epoxypropyl 2-(butoxy)ethyl sulfone, 2-(2,3-epoxyethoxy)ethyl 2-(methoxy)ethyl sulfone, and the like; et cetera. Thepreferred sulfones for use in the treatment of this invention are thosewherein the acid-reacting group is a terminal vie-epoxy group and thebase-reacting group is a ,B-hydroxyalkyl group because of their greaterreactivity in the cross-linking treatment.

These difunctional sulfones are produced by the reaction of organicperacids with olefinically unsaturated compounds of the formula RXCH (RO),,R wherein R, R and n are as defined above; R is an alkenyl radi calof from 2 to about 8 carbons, inclusive; and X is a divalent thio (S),sulfinyl (-SO) or sulfonyl (SO group. As examples of suitable compoundsof this type one can mention allyl vinyl sulfide, 3-butenyl vinylsulfide, crotyl vinyl sulfide, 2-hexenyl vinyl sufide, S-hexenyl vinylsulfide, 2-(vinyloxy)ethyl vinyl sulfide, 2-(vinylo-xy) propyl vinylsufide, 2-(vinyloxy)-1-methylpropyl vinyl sulfide,2-(vinyloxy)-l-methylpropyl vinyl sulfide, 2- (allyloxy)ethyl vinylsulfide, 2-(5-hexenyloxy)ethyl vinyl sulfide, allyl 2-hydroxyethy1sufide, allyl Z-hydroxypropyl sulfide, allyl 2-hydroxy-1-methylpropylsulfide, 2-(allyloxy)ethyl 2-hydroxyethyl sulfide, allyl Z-(methyloxy)ethyl sulfide, allyl 2-(ethoxy)ethyl sulfide, allyl 2-(butoxy)ethylsulfide, 2-(alloxy)ethyl 2-(methoxy)ethyl sulfide and the like, as wellas the corresponding sulfoxides and sulfones. These unsaturatedprecursors are readily prepared by reacting a mercaptoalcoh-ol, forexample, mercaptoethanol, with a monoolefinic halide, for example allylchloride, to produce a hydroxyalkyl alkenyl sulfide, for example2-hydroxyethyl allyl sulfide; divinyl sulfide is reacted with water toproduce vinyl Z-hydroxyethyl sulfide, which is reacted with an alkenylhalide to produce a vinyl (alkenyloxy)ethyl sulfide; and the like.

The peracids which are employed to produce the sulfones are aliphatic,cycloaliphatic and aromatic peracids, including peracetic acid,perpropionic acid, perbutyric acid, perhexanoic acid, perdodecanoicacid, perbenzoic acid, monoperphthalic acid and the like. The loweraliphatic hydrocarbon peracids having from 2 to 4 carbon atoms arehighly suitable, with peracetic acid being the most preferred.

The reaction is conducted by adding a 10 to 50 weight percent,preferably 20 to 40 weight percent, solution of the peracid in a solventsuch as ethyl acetate, butyl acetate or acetone to the olefinicallyunsaturated compound at a temperature of from C. or lower to about 100C. or higher; preferably from about 25 C. to about 75 C. The amount ofperacid employed should be in excess of the stoichiometric amountrequired to oxidize the thio or sulfinyl group, if present, to thesulfonyl group, and to epoxidize the olefinic double bond. When asulfide or sulfoxide is employed as the precursor it is preferred that aportion of the peracid be added at a temperature of from about 15 C. toabout 35 C. for the oxidation of the thio or sulfinyl group to thesulfonyl group, and that the balance of the peracid be added at atemperature of from about 40 C. to about 70 C. to epoxidize the doublebond. Under these conditions the vinyl group attached to the sulfonylgroup will not epoxidize. The difunctional sulfone is separated from themixture by known techniques.

The fabric teratment of this invention essentially comprises reactingthe sulfone with the cellulosic fabric under either acidic or basicconditions to produce a presensitized fabric having properties similarto the untreated fabric. The presensitized fabric is then heated underbasic or acidic conditions to cross-link the cellulose and produce awrinkle-resistant, wash-and-Wear cotton fabric.

The first step of the process of this invention consists of impregnatingthe fabric with the sulfone and curing catalyst and curing theimpregnating fabric to obtain a fabric having from about 2 to about 15,preferably from 3 to about 12, weight percent reacted difunctionalsulfone, based on the weight of the untreated fabric. The impregnationis readily accomplished by conventional techniques wherein the fabric isimmersed in an aqueous solution of sulfone and either a basic or anacidic curing catalyst.

The concentration of the sulfone in the aqueous bath is not critical,and can vary from as low as 3 percent or less up to about 25 percent ormore. When the sulfone is present in such concentrations the desireddegree of addon can be obtained by padding the fabric to about 100percent Wet pick-up, based on the weight of the fabric, and then dryingand curing the fabric.

When an acid catalyst is employed in the first step, the reaction oncuring occurs between the epoxy group of the sulfone and a hydroxylgroup of the cellulosic fabric to provide cellulosic molecules havingpendant vinylsulfonyl, ,B-hydroxyalkylsulfonyl or B-alkoxyalkylsulfonylgroups. This product can be represented by the general formula ZHUOHtORCH SO R] wherein R, R and n are as defined above; Z represents thegellulgsic fabric; and y is an integer,

The acid catalysts which are employed in efiecting this reaction arelatent acid catalysts; i.e., compounds which liberate acidic componentsat temperatures of from about C. to about 200 C. As examples of suitablelatent acid catalysts one can mention Lewis acids such as stannicchloride, zinc chloride, aluminum chloride, ferric chloride and thelike; Lewis acid complexes, such as etherates and amine complexes,including piperadine-boron trifiuoride, monoethylamine-borontrifluoride, boron trifluoride etherates and the like; fiuoroboratesalts of metals such as magnesium fluoroborate, tin fluoroborate,cadmium fiuoroborate, sodium fiuoroborate, zinc fiuoroborate, and thelike; stannous and stannic acylates; stannous alkoxides; et cetera, aswell as acid catalysts which have been encapsulated with materialsmelting at 100200 C., such as in disclosed in US. Patent No. 3,018,258.

The amount of acid catalyst in the bath is not critical provided asolution having a pH of about 6 or below is obtained. However, amountsof from about 1 to about 10, preferably from about 2 to about 5, weightpercent, are generally suitable. At low pH (3 or less), the epoxy groupof the sulfone is susceptible to hydrolysis, thus reducing theefficiency of the cross-linking. For this reason it is desirable toinclude a buffering agent in the acid bath to maintain a pH of fromabout 5 to about 6. As examples of suitable buffers one can mention zincoxide, magnesium oxide, ammonium hydroxide, Zinc acetate and the like.

When a basic catalyst is employed in the first step, the reaction oncuring occurs between the vinyl, hydroxyalkyl or alkoxyalkyl group ofthe sulfone and a hydroxy group of the cellulosic fabric. The product ofthis step can be represented by the formula [ZOR S() CI-l (OR R whereinZ, R R n and y are as defined above and R is a divalent a,fl-alkylenegroup of from 2 to 4 carbons.

The basic catalysts which are employed are strong bases such ashydroxides of sodium or potassium, or quaternary ammonium hydroxidessuch as tetramethylammonium hydroxide, benzyl trimethylammoniumhydroxide and the like; or sodium or potassium salts of inorganic acidshaving a dissociation constant of less than 5 10 such as sodiumcarbonate, potassium carbonate, sodium bicarbonate, potassiumbicarbonate, disodium hydrogen phosphate, dipotassium hydrogenphosphate, trisodium phosphate, tripotassium phosphate and the like.

The amount of basic catalyst in the aqueous bath is not critical,provided the bath has a pH of at least about 8, and preferably at leastabout 10. In general, amounts of base of from about 1 to about 10,preferably from about 2 to about 5 weight percent are sufficient.

The curing of the impregnated fabric is achieved by heating at fromabout C. to about 200 C. If desired, the fabric can be dried at lowertemperatures such as 50 C. to 100 C. to remove the water prior tocuring. After curing the fabric, the treated fabric is then scoured toremove unreacted difunctional sulfone and curing catalyst. The scouringis effected by Washing the fabric in hot (about F.) water containing asmall quantity of detergent. The resulting presensitized fabric can bestored for extended periods of time or can be immediately subjected tothe final cross-linking step.

The final cross-linking is accomplished by impregnating the treatedfabric with a curing catalyst which is acidic if the catalyst employedin the first step was basic, or is baisc if the catalyst in the firststep was acidic. The impregnation is accomplished in a manner similar tothat employed in the first step; i.e., padding the fabric to about 100weight percent wet pick-up in an aqueous solution containing from about1 to about 10, preferably from about 2 to about 5, weight percentdissolved catalyst. After drying, the fabric can be stored or can beimmedis ately heated to a temperature of from about 120 C. to about 200C. to ef ect the. final c oss-link ng. c u e the rate of reaction, inthe absence of any catalyst, is relatively slow at temperatures of lessthan about 170 180 C., the fabric without catalyst can be pressed attemperatures of from 100 C. to 170 C. for up to five minutes withoutobtaining a high degree of cross-linking. Thus, if errors are made inpressing, the garment can be readily repressed before the final cure.

Although the first step can be either the acid-catalyzed orbase-catalyzed reaction, it is preferred to employ the acid-catalyzedstep first, particularly if the resulting presensitized fabric is to bestored for extended periods of time. If the base-catalyzed process isemployed first, the treated fabric must be thoroughly washed to ensurethat all of the catalyst, which would neutralize the latent acidcatalyst, is removed from the fabric. In addition, the pendant vinyl,alkoxy or hydroxyl groups in the treated fabric resulting from theacid-catalyzed first step are more stable than the pendant epoxidegroups resulting from a base-catalyzed first step, permitting longerstorage times of the presensitized fabric produced by the acid-catalyzedfirst step.

By the term cellulosic fabric is meant a fabric containing at least 40weight percent cellulose, including cotton, regenerated cellulose,rayon, linen and the like.

The following examples are illustrative. In the evaluation of thetreated fabrics the following tests were employed:

(A) Crease recovery-ASTM D-1295053T (warp direction only).

(B) Wash and wear index.A sample of the fabric is washed and either spundried or tumble dried, and then evaluated as follows:

See Textile Res. 1., 26, 974 (1956) and Amer. Dye Rep, 48, 37 (1959);ASTM Method 88-1960.

(C) Crease rating.A creased fabric was washed and the appearance of thecrease rated on a scale of from 1, indicating no crease, to 5,indicating full retention of the crease.

See 1963 Technical Manual of AATCC, pages A37, A38, Report No. RA-61 onWash and Wear.

EXAMPLE 1 2(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone A mixture of345 grams of allyl chloride and 200 grams of benzene was fed dropwiseover a period of /2 hour to a solution of 312 grams of potassiumhydroxide in 1830 grams of thiodiglycol at 100 C. During this period,water of reaction was removed as an azeotrope with benzene bydistillation. The resulting mixture was heated at 110-115 C. for anadditional hours, at which time all of the water of reaction had beenremoved. After cooling to room temperature and filtering to remove thepotassium chloride formed during the reaction, the reaction mixture wasdistilled to recover 341 grams of 2-(allyloxy)ethyl Z-hydroxyethylsulfide as a fraction boiling at 9095 C. and 1.0 mm. The2-(allyloxy)ethyl Z-hydroxyethyl sulfide had a purity of 99 percent, asdetermined by analysis for olefinic unsaturation with bromine, and apurity of 94.2 percent, as determined by analysis for the hydroxyl groupwith acetic anhydride in pyridine catalyzed with perchloric acid. The2-(all'yloxy)ethyl 2-hydroxyethyl sulfide had a refractive index, n of1.4936 and a molecular weight of 170 (theory 162) as determined by themodified Menzies-Wright method employing acetone.

To 290 grams of 2-(allyloxy)ethyl Z-hydroxyethyl sulfide there wereadded dropwise 2470 grams of a 20 percent solution of peracetic acid inethyl acetate. Two thirds of the solution was added at 25 C. over twohours to oxidize the sulfide to the sulfone, at which time the mixturewas heated to 5060 C. and the remainder of the solution was added overone hour to epoxidize the double bond. After heating the resultingmixture at 50-60 C. for an additional 10 hours the mixture was feddropwise to refluxing ethylbenzene at 50 mm. pressure, whilecontinuously removing acetic acid as an azeotrope with the ethylbenzene.Distillation was continued to a kettle temperature of 60 C. at 3 mm.pressure. The colorless residue remaining in the kettle was 278 grams of2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone having a purity of 84%as determined by epoxide analysis using the pyridine hydrochloridemethod. The 2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone had arefractive index, r1 of 1.4879 and a molecular weight of 217 (theory210).

Analysis.Calcu1ated for C H O S: C, 39.99%; H 6.71%; S, 15.2%.

Found: C, 40.3%; H, 6.6%; S, 14.9%.

EXAMPLE 2 A sample of mercerized cotton print cloth was immersed in asolution of 10 weight percent 2-(2,3-epoxypropoxy)ethyl 2-hydroxyethylsulfone, 2.0 Weight percent zinc fiuoroborate and 0.3 weight percentmagnesium oxide in Water, padded to about weight percent wet pick-up,dried for 3 minutes at 5 C. in a forced-air oven, and cured for 3minutes at C. The fabric was then laundered with a 0.1 Weight percentsolution of a built detergent in water to remove residual reagents andtumble dried. The dry add-0n after laundering was 5.5 weight percent.The crease recovery and the wash and wear index of the treated fabricwere unchanged from the untreated fabric, being about 35 percent and 1,respectively.

A portion of the treated fabric was immersed in a 5 weight percentsolution of sodium carbonate in water, padded to about 100 weightpercent wet pick-up, creased and dried on a tailors press at 96 poundssteam pressure for 5 minutes to a maximum fabric temperature of 140 C.,and then cured for 2 minutes at C. After Washing and tumble drying thetreated fabric was found to have a crease recovery of 67 percent and awash and Wear index of 4.0.

EXAMPLE 3 Employing apparatus, materials and procedures similar to thosedescribed in Example 2, except that after padding with the sodiumcarbonate solution, the fabric was stored for 4 weeks at 70 F. and 65%relative humidity, and then creased and cured, there was obtained afabric having a crease recovery of 66 percent and a wash and wear indexof 4.0.

EXAMPLE 4 In a manner similar to that described in Example 2, a sampleof mercerized cotton print cloth is immersed in an aqueous solution of2,3-epoxypropyl vinyl sulfone, zinc fiuoroborate and magnesium oxide,dried and cured. The treated fabric is then immersed in an aqueoussolution of sodium carbonate, dried and cured, to produce a fabrichaving good wrinkle and shrink resistance and good crease retentionproperties.

EXAMPLE 5 In a manner similar to Example 2, except that 2-(2,3-epoxypropyl)ethy1 2-(ethoxy)ethy1 sulfone is substituted for the2-(2,3-epoxypropoxy)ethyl 2-hydroxyethyl sulfone, there is produced atreated cotton fabric having good wrinkle and shrink resistance and goodcrease retention properties.

EXAMPLE 6 Twelve samples of mercerized cotton print cloth were immersedin a solution of 10 weight percent 2-(2,3- epoxypropoxy)ethylZ-hydroxyethyl sulfone, 2 weight percent zinc fiuoroborate, and 0.3weight percent magnesium oxide in water, padded to about 100 weightpercent wet pick-up, dried for 10 minutes at 40 C. and cured for 3minutes at 150 C. Ten of the treated samples were immersed in a 5 weightpercent solution of sodium carbonate in water and dried for 10 minutesat 40 C. The samples were then treated as follows:

(A) Two were cured for 2 minutes at 180 C.

(B) Two were stored for 4 weeks at 70 F. and 65% relative humidity andthen cured for 2 minutes at 180 C.

(C) Two were creased for 5 minutes on a tailers press at 96 pounds steampressure to a maximum fabric temperature of 140 C.

(D) Two were creased for 5 minutes on a tailors press at 96 pounds steampressure to a maximum fabric temperature of 140 C. and then cured for 2minutes at 180 C.

(E) Two were stored for 4 weeks at 70 F. and 65% relative humidity,creased for 5 minutes on a tailors press at 96 pounds steam pressure toa maximum fabric temperature of 140 C. and then cured for 2 minutes at180 C.

Wash-Wear Index Dry Crease Add-on, Recovery, Tumble Spin Crease Wt.Percent Percent Dry Dry Rating Treatment:

8 What is claimed is: 1. A difunctional sulfone of the formula RSO CH (R0 R wherein R is a member selected from the group consisting ofBhydroxyalkyl of 2 to 4 carbons and B-(alkoxy)-alkyl of 1 to 4 carbonsin the alkoxy group thereof and 2 to 4 carbons in the aikylene groupthereof; R is a divalent alkylene group Of 1 to 3 carbons; R is avic.-epoxyalkyl group of from 2 to 8 carbons; and n is an integer havinga value of from 0 to 1.

2. A difunctional sulfone as described in claim 1 wherein R isfl-hydroxyalkyl of 2 to 4 carbons, R is a divalent alkylene group of 1to 3 carbons, R is a terminal-vie.- epoxyalkyl group of 2 to 8 carbons,and n is l.

3. A difunctional sulfone as described in claim 1 wherein R isfi-hydroxyalkyl of 2 to 4 carbons, R is a terminalvic.-epoxyalkyl groupof 2 to 8 carbons, and n is 0.

4. A difunctional sulfone as described in claim 1 wherein R isfl-hydroxyethyl, R is a methylene group, R is a terminal-vic.-epoxyalkylgroup of 2 to 8 carbons, and n is 1.

5. Z-hydroxyethyl 2-(2,3-epoxypropoxy)ethyl sulfone.

References Cited UNITED STATES PATENTS 3,220,981 11/1965 MacPeek et a1.260348 X OTHER REFERENCES Tesoro, G. C. et al., Textile ResearchJournal, vol. 33,

" No. 2, pp. 93-107 (1963).

NORMA S. MILESTONE, Primary Examiner US. Cl. X.R.

